Bis(vinylsulfonylmethyl) ether



United States Patent 3,539,644 BISWINYLSULFONYLMETHYL) ETHER Donald M. Burness and Charles J. Wright, Rochester,

N.Y., assignors t0 Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 13, 1967, Ser. No. 682,525 Int. Cl. C07c 147/04 US. Cl. 260-607 1 Claim ABSTRACT OF THE DISCLOSURE Compositions of matter comprising certain compounds containing two vinylsulfonylalkyl groups attached to a single heteroatom are disclosed as effective hardening agents for hardenable material. Photographic elements comprising said compounds are also disclosed.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a class of new hardeners and more particularly to hardening compounds containing two vinylsulfonylalkyl groups attached to a single heteroatom. In one aspect, this invention relates to the rendering of compositions of proteins and proteinaceous substances, such as hydrophilic colloids, resistant to the effects of swelling from aqueous solutions. In another aspect it relates to the use of said hardeners in photography and more particularly to photographic elements comprising a layer hardened by said hardeners and exhibiting reduced staining characteristics. In still another aspect it relates to improvements in photographic elements comprising color couplers.

DESCRIPTION OF THE PRIOR ART The use of various hardenable materials, such as proteins and proteinaceous substances, like hydrophilic colloids and more particularly gelatin and certain synthetic carboxyl-containing polymers, alone and in combination with each other, is enhanced by increasing their resistance to swelling from aqueous solutions. These hardenable materials can be advantageously hardened in various forms such as solutions, emulsions and layers as for example in photographic products and elements.

Various materials have been suggested for increasing swell resistance of proteins and proteinaceous materials, like hydrophilic colloids, and although some materials have shown utility, many of them have adversely affected the properties, particularly photographic properties, of substances containing them. In order to improve resistance to aqueous swell or to harden a hardenable material, such as a carboxyl-containing polymer, without adversely affecting its photographic properties, hardening agents containing vinyl sulfones have been incorporated into hardenable materials. For example, certain hardening compounds containing two or more vinylsulfonylalkyl groups linked to a plurality of tertiary or quaternary nitrogen atoms or ether oxygen atoms are disclosed in the prior art. However, these compounds are not readily accessible and their preparation and synthesis generally requires handling of the highly toxic and vesicant divinyl sulfone. Further, as shown by examples hereafter, the compounds of the present invention are significantly more active on a mole for mole basis than prior hardening compounds disclosed in US. patent application Ser. No. 488,797, Burness et al., filed Sept. 20, 1965. It is evident that the art would be advanced by effective, safe and convenient means for providing good swell resistance to hardenable materials, using hardening compounds which neither substantially affect adversely the photographic "ice properties of said materials nor detrimentally affect the individual workers during said compounds preparation.

It is an object of this invention to provide hardening compounds for hardenable material such as proteins, hydrophilic colloids and, more particularly, carboxylcontaining polymers such as gelatin and compositions comprising gelatin.

It is another object to provide hardening compounds useful in photography and for incorporating into photographic elements, which compounds do not possess photographic properties substantially more adverse than known hardeners or cause the harmful physiological effects of prior compounds.

Yet another object of this invention is to provide certain vinylsulfonyl compounds possessing increased hardening activity as compared to known hardening compounds.

It is still another object of this invention to provide vinylsulfonyl hardening compounds having two vinylsulfonylalkyl groups attached to a single linking heteroatom, such as ether oxygen, or a tertiary or a quaternary nitrogen atom.

Other objects will become apparent from the following.

SUMMARY OF THE INVENTION We have now discovered that certain vinylsulfonyl hardening compounds containing two vinylsulfonylalkyl groups linked to a single heteroatom are effective and desirable hardeners. By the term single linking heteroatom is meant an atom chosen from non-metals in Groups VA and VI-A of the Periodic Table, which atoms include, for example, oxygen and nitrogen and which atoms can be substituted or unsubstituted, for example, alkyl nitrogen and dialkyl nitrogen linking atoms and more particularly,

G9 ,R N X Where each R is an alkyl group of l to 4 carbon atoms, and X is an anion such as, for example,

and the like.

In practicing this invention in one of its aspects these hardening compounds are conveniently incorporated into photographic gelatin emulsions and layers thereof in order to provide needed hardening without substantially affecting photographic sensitivity adversely. These new hardening compounds can be effectively used in various concentrations for hardening purposes although a preferred suitable hardening concentration is generally in the range of from about 0.1 to 10% and more preferably about 0.5 to 6% by weight, based on the hardenable material such as the hydrophilic colloid.

As illustrated by the following examples, the hardeners described herein are particularly effective in color photography when combined with color couplers. Their use results in reducing the staining characteristics usually exhibited by multiple layer photographic silver halide systems containing a color coupler and hydrophilic colloid layers. Such layers generally comprise hardenable carboxyl-containing polymers, for example, gelatin, vinyl polymers, or mixtures thereof. Suitable carboxyl-containing polymers are film-forming and suitable vinyl polymers are exemplified by methyl acrylate-acrylic acid polymer, butyl-acrylate-acrylic acid polymer and the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of this invention relates to hardening compounds having two vinylsulfonylalkyl groups linked to a single linking heteroatom or radical.

Another embodiment of this invention relates to a composition of matter comprising a hardenable substance and a hardener having the formula in which in is an integer of from 1 to 4, Z is a single heteroatom, and R is hydrogen or lower alkyl groups such as methyl, ethyl, isopropyl and the like which groups in turn can be further substituted.

Another embodiment of this invention relates to compositions of matter comprising a hydrophilic colloid and a hardener having as the heteroatom, a single nitrogen atom, or ether oxygen.

Still another embodiment relates to a photographic element comprising a support and an emulsion layer comprised of hardenable carboxyl-containing polymer, said emulsion being hardened by an effective concentration of a bis vinylsulfonylalkyl-type compound disclosed herein.

The bis vinylsulfonylalkyl type compounds disclosed herein are effectively used in combination with hardenable materials generally, but find particular use in photography for hardening various proteins, like hydrophilic colloid coating compositions, binders, vehicles and the like, including photographic gelatin emulsions and layers. These layers can take the form of interlayers, overcoats, antihalation layers, silver halide emulsion layers and the like. By photographic gelatin emulsions is meant various gelatin derivatives and physical mixtures of gel atin and other colloids. These include gelatin mixtures of synthetic polymers exemplified by copolymers of methyl acrylate and acrylic acid or butyl acrylate and acrylic acid and the like. The compounds disclosed herein can be conveniently added either in solution or as addition salts to the emulsion or other substance to be hardened.

The reactions for preparing the compounds of this invention are conducted in the presence of the desired organic solvents at moderate temperatures and the reactions are not solely pressure dependent, and consequently, super-atmospheric or subatmospheric pressures can be employed. As is obvious to one skilled in the art, the specific reaction conditions, for example, temperature, pressure, and the like depend upon the particular reactants used.

The compounds described in this application can be used effectively in combination with hardenable materials in general, but they are most advantageously used with natural or synthetic polymers used as vehicles or binders in preparing photographic elements. Specific materials which can be hardened according to the practice of this invention include hardenable materials such as polymers, for example, gelatin, colloidal albumin, acid or watersoluble vinyl polymers, cellulose derivatives, proteins, various polyacrylamides, dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials as exemplified by amine-containing polymers of alkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, maleic acid, and the like. The hardening agents described herein can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic and infrared emulsions, they are also useful in X-ray and other nonoptically sensitized emulsions. They can be added to the emulsions before or after the addition of any optically sensitizing dyes which may be used. They are eifective in sulfur and gold sensitized silver halide emulsions.

The materials hardened in the practice of this invention can be coated on a wide variety of supports. Typical supports include those generally employed for photo graphic elements, as exemplified by cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, and related films.

or resinous materials as well as glass, paper, metal, wood and the like. Supports such as paper that are coated with a-olefin polymers, particularly polymers of u-olefins containing 210 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers, and the like can also be employed.

In addition to the hardening agents disclosed herein, photographic emulsions and elements can also contain ad ditional additives, particularly those known to be beneficial in photographic emulsions, as exemplified by optical sensitizers, speed increasing materials, other hardeners, plasticizers, and the like, such as those described in Henn and Goife US. Pat. 3,128,180 issued Apr. 7, 1964.

The emulsions hardened by our new compounds can be used in photographic elements intended for color photography and thus can contain color-forming couplers or used as emulsions to be developed by solutions containing couplers or other color-generating materials or emulsions of the mixed-packet type.

The silver halides employed in the photographic emulsions include any of the photographic silver halides as exemplified by silver bromide, silver iodide, silver chloride, silver chloroiodine, and the like. The silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide emulsion.

Hardened emulsions obtained in accordance with this invention and with gelatin or other hardenable hydrophilic colloids can be used in diffusion transfer materials.

This invention can be further illustrated by the following examples of preferred embodiments thereof although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

EXAMPLE I Bis(2-vinylsulfonylethyl) ether 6 oxa 3,9 dithiaundecane 1,11 diol is prepared by the reaction of two molar proportions of sodium 2- hydroxyethylmercaptide with bis(2-chloroethyl) ether in methanol, followed by evaporation of the solvent.

The disulfide is oxidized to the disulfone by hydrogen peroxide according to the method of H. S. Schultz et al., J. Org. Chem., 28, 1140 (1963). The resulting diol is converted to 2,2-bis(Z-chloroethylsulfonyl) ethyl ether by adding two molar proportions of thionyl chloride to a refluxing solution of the diol in acetonitrile containing a catalytic amount of N,N,-dimethylformamide. When the reaction is complete, removal of the solvent and recrystallization from ethanol-acetone gives a high yield of a colorless chloride having a melting point of 70- 71 C.

Dehydrohalogenation is effected in tetrahydrofuran solution at about 0-5" C. with two molar proportions of triethylamine. After 24 hours, the solvent is removed and the product recrystallized from methanol giving colorless crystals having a melting point of 47.5-48.5 C.

EXAMPLE II Bis (vinylsulfonylmethyl) ether Following the procedure of Example I, and starting with bis(chloromethyl) ether, the colorless intermediate chloride is prepared having a melting point of 8384 C. A similar process of dehydrohalogenation as in Example I and subsequent recrystallization from a methanolethanol mixture yields a colorless product with a melting point of 41.5-42.5 C.

EXAMPLE III Bis(4-vinylsulfonylbutyl) ether Following the procedure of Example I and starting with bis(4-chlorobutyl) ether, a colorless intermediate chloride is prepared having a melting point of 66-68 C. Dehydrohalogenation, as in Example I, carbon decolorization in methanol solution and evaporation of the methanol under reduced pressure yields a pale yellow oily product of 11 1.5023.

EXAMPLE IV N,N-bis (2-vinylsulfonylethyl) -n-propylamine The dropwise addition of a tetrahydrofuran solution of n-propylamine to two molar proportions of divinyl sulfone dissolved in tetrahydrofuran at a temperature maintained at 10 C. yielded, after two hours stirring at room temperature and evaporation of the solvent at reduced pressure, a pale tan product of 11 14917.

Other bis vinylsulfones exhibiting good hardening include N,N bis(2 vinylsulfonylethyl) N ethyl-N- propylammonium tetrafiuoroborate, and bis(l vinylsulfonylethyl) ether.

EXAMPLE V As previously indicated, the hardening compounds described herein give very good results when used to harden hydrophilic colloids, for example, gelatin compositions and more particularly photographic silver halide gelatin emulsions. To illustrate this, the compound prepared in the above Example I is added to separate sample portions of a high-speed silver bromoiodide emulsion which is panchromatically sensitized with a cyanine dye.

Each emulsion sample is coated on a cellulose acetate film support at a coverage of 459 milligrams of silver and 1040 milligrams of gelatin per square foot. A sample of each film coating is then exposed on an Eastman 1B Sensitometer, processed for five minutes in Kodak DK-SO Developer, fixed, washed and dried. Results are recorded for sensitometric efiect of these compounds as compared to a control and to a prior art hardening compound l,2-bis(2-vinylsulfonyleth0xy) ethane. Similar good results are obtained with the other hardening compounds of this invention including those of Example IV.

as follows; a decrease indicating water-impermeability and hardening:

EXAMPLE VI Samples of the above compounds are placed into three color-incorporated color coupler coatings of the type described in US. Pat. 2,956,879 of Van Campen, issued Oct. 18, 1960. They are used in various concentrations of from about 0.1 to 2.6% by weight of the dry gelatin and compared to a control of a known hardener, mucochloric acid, in 0.55% concentration and the hardener of US. application Ser. No. 488,797 of Burness, Cowan and Wright, filed Sept. 20, 1965, 1,2-bis(2-vinylsulfonylethoxy) ethane in 2-3% concentration.

The coatings are tested for hardness after 1 day, 5 days after coating and upon heating with a p-phenylenediamine color developing solution at 10 C. intervals from 30 C. to 80 C., then immersing each test strip in the solution during the entire heating cycle and holding the bath temperature for 2 minutes at each interval. This is followed by rubbing or scratching through a rubber glove after each interval.

The results are as follows:

PERCENT BY WEIGHT OF DRIED GELATIN The resistance to swell, relative speed, contrast and fog are determined and are as follows:

TABLE I TABLE II A sample of each film coating is tested for hardness after three days incubation at 120 F. and relative humidity, by immersing in water at 25 C. for 3 minutes and calculating percentage swell of the emulsion Those samples marked (A) and (B) are equimolar, respectively, with other similarly marked samples and the results of this example clearly show the significantly greater hardening activity, mole for mole, of the compounds of the present invention as compared to those known in the art. In addition, improvement in stain is noted by using the present hardeners as compared with other known hardeners such as mucochloric acid.

Silver halide emulsions containing the hardners of the invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer. Such processes are described in US Pats. 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951; and 3,020,155 of Yackel, Yutzy, Foster and Rasch issued Feb. 6, 1962. The emulsions can also be used in diffusion transfer color processes which utilize a ditfusion transfer of an imagewise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another. Such processes are described in Rogers US. Pat. 2,983,606 issued May 9, 1961; Weyerts et al. US. Pat. 3,253,915 issued May 31, 1966; and Whitmore US. Pat. 3,227,552 issued Jan. 4, 1966. Silver halide emulsions containing the hardeners of the invention can be processed in stabilization processes such as the ones described in US. Pat. 2,614,927 of Broughton and Woodward issued Oct. 21, 1952, and as described in the article Stabilization Processing of Films and Papers, by H. D. Russell, E. C. Yackel and I. S. Bruce in P.S.A. Journal, Photographic Science and Technique, vol. 16B, October 1950.

The hardeners of this invention can be used to harden silver halide emulsion and other photographic layers containing silver halide developing agents such as polyhydroxy benzene, amino phenol and 3-pyrazolidone developing agents.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it Will be understood that variations 8 and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claim.

We claim: 1. Bis(vinylsulfonylmethyl) ether.

References Cited FOREIGN PATENTS 985,150 3/1965 Great Britain.

CHARLES B. PARKER, Primary Examiner R. L. RAYMOND, Assistant Examiner US. Cl. X.R. 

